Nashrieh Shimi va Mohandesi Shimi Iran

Nashrieh Shimi va Mohandesi Shimi Iran

Chemical fixation of carbon dioxide to cyclic carbonates using covalent triazine frameworks

Document Type : Research Article

Authors
Mozhdeh Pourmansouri 1
Mojtaba Khorasani 1, 2
1 Faculty of Chemistry, Zanjan University of Advanced Studies in Basic Sciences, Zanjan, I.R. IRAN
2 Research Institute of Basic Sciences and New Technologies, Zanjan University of Basic Sciences, Zanjan, I.R. IRAN
Abstract
Recyclable solid catalysts based on hydrogen-bond donor (HBD) groups have been rarely explored for the cycloaddition of CO2 to epoxides, despite their inherent advantages such as high efficiency and the absence of metal species. Herein, we report a covalent triazine framework (CTF) incorporating amide units as a recyclable organocatalyst for this reaction. The catalyst was readily synthesized via a condensation reaction between inexpensive and readily available precursors, melamine and dipicolinic acid, in dimethyl sulfoxide at 140 °C. Following structural characterization and confirmation of the CTF formation, its catalytic performance was first evaluated in the model reaction of CO2 with styrene oxide. Investigation of the reaction parameters revealed that the optimal conditions were 50 mg of CTF, 0.5 mol% tetrabutylammonium bromide (TBAB) as a co-catalyst, a CO2 pressure of 10 bar, and a temperature of 100 °C. Under these optimized conditions, a range of terminal epoxides was successfully converted into their corresponding cyclic carbonates in excellent yields. Furthermore, the catalyst demonstrated excellent recyclability, maintaining its catalytic activity without a significant loss in yield over six consecutive runs.
Keywords
Covalent triazine framework
hydrogen-bond donor catalyst
carbon dioxide transformations
cyclic carbonates
Subjects
[1] Vollenweider J., The Effectiveness of International Environmental Agreements, Int. Environ. Agreements, 13: 343-367 (2013).
[2] Erdogdu E., The Carbon Border Adjustment Mechanism: Opportunities and Challenges for Non-EU Countries, WIREs Energy Environ, 14: e70000 (2025).
[3] Rath B.B., Krause S., Lotsch B. V., Active Site Engineering in Reticular Covalent Organic Frameworks for Photocatalytic CO2 Reduction, Adv. Funct. Mater, 34: 2309060 (2024).
[4] Kamphuis A.J., Picchioni F., Pescarmona P.P., CO2-fixation into Cyclic and Polymeric Carbonates: Principles and Applications, Green Chem, 21: 406-448 (2019).
[5] Laserna V., Fiorani G., Whiteoak C.J., Martin E., Escudero-Adan E.C., Kleij A.W., Carbon Dioxide as a Protecting Group: Highly Efficient and Selective Catalytic Access to Cyclic cis-Diol Scaffolds, Angew. Chem. Int. Ed, 53: 10416-10419 (2014).
[6] Song Q.-W., Ma R., Liu P., Zhang K., He L.-N., Recent Progress in CO2 Conversion into Organic Chemicals by Molecular Catalysis, Green Chem, 25: 6538-6560 (2023).
[7] Liu R., Tan K.T., Gong Y., Chen Y., Li Z., Xie S., He T., Lu Z., Yang H., Jiang D., Covalent Organic Frameworks: An Ideal Platform for Designing Ordered Materials and Advanced Applications, Chem. Soc. Rev, 50: 120-242 (2021).
[8] Guo J., Jiang D., Covalent Organic Frameworks for Heterogeneous Catalysis: Principle, Current Status, and Challenges, ACS Cent. Sci, 6: 869-879 (2020).
[9] Liu M., Guo L., Jin S., Tan B., Covalent Triazine Frameworks: Synthesis and Applications, J. Mater. Chem. A, 7: 5153-5172 (2019).
[10] Li H., Dilipkumar A., Abubakar S., Zhao D., Covalent Organic Frameworks for CO2 Capture: From Laboratory Curiosity to Industry Implementation, Chem. Soc. Rev, 52: 6294-6329 (2023).
[11] Peter S.E., Thomas P., Vairavel P., Kumar N.A.V., Cyanuric Chloride as a Linker Towards the Synthesis of Covalent Triazine Polymers: A Review, Mater. Adv, 5: 9175-9209 (2024).
[12] Qian Z., Wang Z.J., Zhang K.A.I., Covalent Triazine Frameworks as Emerging Heterogeneous Photocatalysts, Chem. Mater., 33: 1909-1926 (2021).
[13] Liu N., Xie Y.-F., Wang C., Li S.-J., Wei D., Li M., Dai B., Cooperative Multifunctional Organocatalysts for Ambient Conversion of Carbon Dioxide into Cyclic Carbonates, ACS Catal, 8: 9945-9957 (2018).
[14] Liu M., Lu X., Jiang Y., Sun J., Arai M., Zwitterionic Imidazole-Urea Derivative Framework Bridged Mesoporous Hybrid Silica: A Highly Efficient Heterogeneous Nanocatalyst for Carbon Dioxide Conversion, ChemCatChem, 10: 1860-1868 (2018).
[15] Wang X., Yang L., Chen Y., Yang C., Lan J., Sun J., Metal-Free Triazine-Incorporated Organosilica Framework Catalyst for the Cycloaddition of CO2 to Epoxide under Solvent-Free Conditions, Ind. Eng. Chem. Res, 59: 21018-21027 (2020).
[16] Bansal A., Sharma R., Mohanty P., Nanocasted Polytriazine-SBA-16 Mesoporous Composite for the Conversion of CO2 to Cyclic Carbonates, J. CO2 Util, 40: 101189 (2020).
[17] Liu M., Zhao P., Ping R., Liu F., Liu F., Gao J., Sun J., Squaramide-Derived Framework Modified Periodic Mesoporous Organosilica: A Robust Bifunctional Platform for CO2 Adsorption and Cooperative Conversion, Chem. Eng. J, 399: 125682 (2020).
[18] Cheng X., Zhao P., Zhang M., Wang S., Liu M., Liu F., Fabrication of Robust and Bifunctional Cyclotriphosphazene-Based Periodic Mesoporous Organosilicas for Efficient CO2 Adsorption and Catalytic Conversion, Chem. Eng. J, 418: 129360 (2021).
[19] Wang Y., Duan J., Urea and Thiourea-Functionalized, Pyridinium-Based Ionic Polymers Convert CO2 to Cyclic Carbonate under Mild Conditions, ACS Appl. Polym. Mater, 4: 5851-5860 (2022).
[20] Tariq W., Pudukudy M., Shuangjiang L., Liu Y., Su H., Li X., Zhi Y., Shan S., A Nitrogen-Rich Organic Polymer for CO₂ Utilization and Conversion Through Cycloaddition of CO2 with Epoxides, React. Funct. Polym, 216: 106412 (2025).
[21] Gao T., Xu F., Tao X., Synthesis of Hydrogen-Bond-Donor-Containing Ionic Covalent Organic Frameworks for Carbon Dioxide Upgrading, J. Colloid Interface Sci, 704: 139337 (2026).
[22] Thommes M., Kaneko K., Neimark A.V., Olivier J.P., Rodriguez-Reinoso F., Rouquerol J., Sing K.S.W., Physisorption of Gases, with Special Reference to the Evaluation of Surface Area and Pore Size Distribution (IUPAC Technical Report), Pure Appl. Chem, 87: 1051-1069 (2015).
[23] Liu Y., Li S., Chen Y., Li M., Chen Z., Hu T., Shi L., Pudukudy M., Shan S., Zhi Y., Urea/Amide-Functionalized Melamine-Based Organic Polymers as Efficient Heterogeneous Catalysts for CO2 Cycloaddition, Chem. Eng. J, 474: 145918 (2023).